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EP2152760B1 - Caoutchoucs nitrile - Google Patents

Caoutchoucs nitrile Download PDF

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Publication number
EP2152760B1
EP2152760B1 EP08759716A EP08759716A EP2152760B1 EP 2152760 B1 EP2152760 B1 EP 2152760B1 EP 08759716 A EP08759716 A EP 08759716A EP 08759716 A EP08759716 A EP 08759716A EP 2152760 B1 EP2152760 B1 EP 2152760B1
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EP
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Prior art keywords
nitrile rubber
coagulation
nitrile
sodium
pentamethylheptane
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German (de)
English (en)
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EP2152760A1 (fr
Inventor
Werner Obrecht
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/14—Coagulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/14—Coagulation
    • C08C1/15—Coagulation characterised by the coagulants used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/14—Coagulation
    • C08C1/16—Coagulation in floc form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds

Definitions

  • the invention relates to a nitrile rubber, a process for its preparation, vulcanizable mixtures based on this nitrile rubber, furthermore a process for the preparation of vulcanizates from these mixtures and the vulcanizates obtained thereby.
  • Nitrile rubbers also abbreviated to "NBR”, are understood to mean rubbers which are copolymers or terpolymers of at least one ⁇ , ⁇ -unsaturated nitrile, at least one conjugated diene and optionally one or more further copolymerizable monomers.
  • storage stability means that the Mooney viscosity, as an important specification criterion for nitrile rubbers, changes as little as possible during long storage times and in particular also at relatively high temperatures, which can occur in summer.
  • Nitrile rubbers and processes for making such nitrile rubbers are known, see eg W. Hofmann, Rubber Chem. Technol. 36 (1963) 1 and Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft, Weinheim, 1993, pp. 255-261 , There is no indication in these publications as to whether and, if appropriate, how to improve the storage stability of nitrile rubbers.
  • JP 75,105,746 describes heat-resistant nitrile rubbers obtained by performing latex coagulation with a mixture of tin dichloride and calcium chloride. Per 100 parts by weight of calcium chloride while 50 parts by weight of tin dichloride are used.
  • tin salts is today problematic for environmental reasons, especially since these tin salts can be found in a comprehensive subsequent washing of the nitrile rubber in nitrile rubber. The removal of tin salts from the wash water is associated with a high and therefore-also undesirable cleaning.
  • JP 76 / 26,790 It is known to coagulate a nitrile rubber latex using strontium chloride, resulting in a coagulated nitrile rubber having a strontium content of 1.2%. It is stated that a molded article prepared based on such a nitrile rubber has much better properties than a corresponding nitrile rubber-based molded article obtained from the latex by coagulation with calcium chloride.
  • NBR is prepared by emulsion polymerization, initially obtaining an NBR latex.
  • the NBR solid is isolated from this latex by coagulation.
  • salts and acids are used for coagulation.
  • the coagulation of latices with metal salts is known that monovalent metal ions, for example in the form of sodium chloride, significantly larger amounts of electrolyte are required than polyvalent metal ions, for example in the form of calcium chloride, magnesium chloride or aluminum sulfate ( Colloid-Z. 154, 154 (1957 )).
  • monovalent metal ions for example in the form of sodium chloride
  • polyvalent metal ions for example in the form of calcium chloride, magnesium chloride or aluminum sulfate ( Colloid-Z. 154, 154 (1957 )).
  • Houben-Weyl (1961) Methods of Org. Chemistry, Macromolecular Substances 1, p.
  • Out DD 154 702 discloses a process for the radical copolymerization of butadiene and acrylonitrile in emulsion, which is controlled by a special, computer-aided dosing program for the monomers and the molecular weight regulator, such as tert-dodecyl mercaptan, and in which the latices obtained by coagulation in an acidic medium for Solid rubber be worked up.
  • the molecular weight regulator such as tert-dodecyl mercaptan
  • the butadiene-acrylonitrile copolymers having 10-30 wt.% Of acrylonitrile obtained are said to have good elasticity and low temperature properties combined with increased swelling resistance and processability. Measures by which an influence on the storage stability of the nitrile rubber is possible can not be deduced from the teaching of this patent.
  • JP 27902/73 (Appl. 69 32.322 ) it is known that the use of amines in the coagulation of latices with magnesium salts, for example by combining diethylenetriamine and magnesium chloride, reduces the scorch rate and thus improves the scorch resistance of nitrile rubbers.
  • magnesium salts for example by combining diethylenetriamine and magnesium chloride
  • DE-OS 24 25 441 in the electrolytic coagulation of rubber latices as an auxiliary instead of the methylcellulose 0.1-10 wt.% (relative to the rubber) of water-soluble C 2 -C 4 alkylcelluloses or hydroxyalkylcelluloses in combination with 0.02 to 10 wt.% (based on the rubber ) of a water-soluble alkali, alkaline earth, aluminum or zinc salt.
  • sodium chloride is used as the preferred water-soluble salt.
  • the coagulum is mechanically separated, optionally washed with water and the remaining water removed. Again, it is stated that the foreign matter as in the DE-OS 23 32 096 when the coagulum is separated, virtually completely removed together with the water, and any remaining residues are washed out completely by washing with further water.
  • DE-OS 30 43 688 it is also the goal of DE-OS 30 43 688 to reduce the amounts of electrolyte required for coagulation of the latex as much as possible. This is done according to the teaching of DE-OS 30 43 688 achieved by using in the electrolytic coagulation of latices in addition to the inorganic coagulant as an aid either on plant-derived proteinaceous materials or polysaccharides such as starch and optionally water-soluble polyamine compounds.
  • inorganic coagulants preference is given to describing alkali metal or alkaline earth metal salts. Due to the special additives, it is possible to reduce the quantities of salt necessary for quantitative latex coagulation.
  • DE-OS 3,043,688 There is no indication as to how an improvement in the storage stability can be achieved by the preparation and / or work-up of the nitrile rubber.
  • EP-A-1 369 436 The goal of EP-A-1 369 436 is to provide nitrile rubbers of high purity.
  • the procedure of EP-A-1 369 436 is based on typical nitrile rubbers. None is done about the polymerization process except that an emulsion polymerization is carried out in the presence of fatty acid and / or resin acid salts as emulsifiers. This is followed by latex coagulation with acids, optionally with the addition of precipitants.
  • acids it is possible to use all mineral and organic acids which make it possible to set the desired pH values.
  • additional precipitants can be used, are called for this alkali salts of inorganic acids such as sodium chloride and sodium sulfate.
  • EP-A-0 692 496 Nitrile rubbers based on an unsaturated nitrile and a conjugated diene are described in each case. Common to all nitrile rubbers is that they contain 10-60% by weight of unsaturated nitrile and have a Mooney viscosity in the range of 15-150, or respectively EP-A-0 692 496 of 15-65 and all having at least 0.03 moles of a C 12 -C 16 alkylthio group per 100 moles of monomer units, said alkylthio group including at least three tertiary C atoms and a sulfur atom directly attached to at least one of the tertiary C atoms is bound.
  • the preparation of the nitrile rubbers is carried out in the presence of a correspondingly constructed C 12 -C 16 -alkylthiol as a molecular weight regulator, which acts as a "chain transfer agent” and is thus incorporated as an end group in the polymer chains.
  • the process for their preparation differs from that of EP-A-0 692 496 in that only 30-80% by weight of the total amount of monomer is used at the beginning of the polymerization and the remaining amount of monomer is metered in only at a conversion of the polymerization of 20-70% by weight.
  • nitrile rubbers according to EP-A-0 779 301 is stated to have 3-20 wt.% of a low molecular weight fraction having a number average molecular weight M n less than 35,000.
  • the process for their preparation differs from that of EP-A-0 692 496 in that only 10-95% by weight of the alkylthiol before the polymerization into the monomer mixture are mixed and the remaining amount of the alkylthiol is added only when a polymerization conversion of 20-70 wt.% Is reached.
  • EP-A-0 692 496 discloses that any coagulants can be used.
  • inorganic coagulants calcium chloride and aluminum chloride are mentioned and used.
  • the focus is on nitrile rubbers which are substantially halogen-free and are obtained by conducting the latex coagulation in the presence of a nonionic surfactant and using halogen-free metal salts such as aluminum sulfate, magnesium sulfate and sodium sulfate.
  • the coagulation is indicated using aluminum sulfate or magnesium sulfate.
  • the resulting substantially halogen-free nitrile rubber has a halogen content of not more than 3 ppm.
  • EP-A-0 692 496 For the preparation of these nitrile rubbers, it is according to EP-A-0 692 496 .
  • EP-A-0 779 300 such as EP-A-0 779 301 It is essential that alkylthiols in the form of the compounds 2,2,4,6,6-pentmethylheptane-4-thiol and 2,2,4,6,6,8,8-heptamethylnonan-4-thiol are used as molecular weight regulators. It is clearly pointed out that when using the conventional known tert-dodecyl mercaptan nitrile rubbers with poorer properties are obtained as regulators.
  • EP-A-0 779 300 such as EP-A-0 779 301
  • Nitrile rubbers produced are claimed to possess a favorable property profile, good processability of the rubber compounds and low mold contamination during processing.
  • the resulting vulcanizates should have a good combination of low temperature and oil resistance and have good mechanical properties. It is further asserted that at the production of nitrile rubbers by high polymerization conversions of greater than 75%, preferably greater than 80% high productivity can be achieved and also the vulcanization rate in the vulcanization with sulfur or peroxides is high, especially in NBR types for injection molding. It is further stated that the nitrile rubbers have a short scorch time and a high crosslink density. About the property of storage stability is made in the said patent applications no statement.
  • the object of the present invention was thus to provide nitrile rubbers which have a good storage stability and at the same time have good properties during processing, ie a good vulcanization profile.
  • the following method has been used and is used in the context of this invention: 0.5 g of the nitrile rubbers are digested by dry ashing at 550 ° C. in a platinum crucible with subsequent dissolution of the ash in hydrochloric acid. After appropriate dilution of the digestion solution with deionized water, the calcium content is determined by ICP-OES (inductively coupled plasma-optical emission spectrometry) at a wavelength of 317.933 nm against calibration matrix adapted calibration solutions. Depending on the concentration of the elements in the digestion solution or sensitivity of the measuring instrument used, the concentrations of the sample solutions for the respective wavelengths used are adapted to the linear range of the calibration ( B. Welz "Atomic Absorption Spectrometry", 2nd ed., Verlag Chemie, Weinheim 1985 )
  • the nitrile rubbers according to the invention preferably have a calcium content of at least 200 ppm, more preferably of at least 400 ppm, most preferably of more than 500 ppm, in particular of at least 600 ppm and more preferably of at least 800 ppm of calcium, based on the nitrile rubber.
  • the nitrile rubbers according to the invention have the desired very good storage stability and at the same time have a positive processing behavior.
  • Storage stability of a rubber is understood to mean the greatest possible constancy of the molecular weight or Mooney viscosity over a relatively long period of time, and in particular also at relatively high temperatures.
  • the storage stability is usually determined by storing the unvulcanized nitrile rubber at a higher temperature over a defined period of time (also referred to as hot air storage) and determining the difference in Mooney viscosities before and after this storage at elevated temperature. Since the Mooney Viscosity of nitrile rubber usually increases in the hot air storage, the storage stability is characterized by the difference in Mooney viscosity after storage minus Mooney viscosity before storage.
  • Mooney viscosity (ML 1 + 4 @ 100 ° C.) are determined in each case by means of a shear disk viscometer in accordance with DIN 53523/3 or ASTM D 1646 at 100 ° C.
  • LS is a maximum of 5 Mooney units.
  • LS is less than 5 Mooney units, more preferably at most 4 Mooney units.
  • the nitrile rubbers according to the invention have repeating units of at least one ⁇ , ⁇ -unsaturated nitrile, at least one conjugated diene and optionally one or more further copolymerizable monomers.
  • the conjugated diene can be of any nature. Preference is given to using (C 4 -C 6 ) -conjugated dienes. Particular preference is given to 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperylene, 1,3-pentadiene or mixtures thereof. Particular preference is given to 1,3-butadiene and isoprene or mixtures thereof. Very particular preference is given to 1,3-butadiene.
  • any known ⁇ , ⁇ -unsaturated nitrile can be used, preferred are (C 3 -C 5 ) - ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile, methacrylonitrile, 1-chloroacrylonitrile, ethacrylonitrile or mixtures thereof. Particularly preferred is acrylonitrile.
  • a particularly preferred nitrile rubber is thus a copolymer of acrylonitrile and 1,3-butadiene.
  • one or more other copolymerizable monomers may be used, e.g. ⁇ , ⁇ -unsaturated mono- or dicarboxylic acids, their esters or amides.
  • nitrile rubbers are also commonly referred to as carboxylated nitrile rubbers or, for brevity, "XNBR".
  • ⁇ -unsaturated mono- or dicarboxylic acids for example, fumaric acid, maleic acid, acrylic acid, methacrylic acid, crotonic acid and itaconic acid can be used. Preference is given to maleic acid, acrylic acid, methacrylic acid and itaconic acid.
  • esters of the ⁇ , ⁇ -unsaturated carboxylic acids are alkyl esters, alkoxyalkyl esters, hydroxyalkyl esters or mixtures thereof.
  • alkyl esters of the ⁇ , ⁇ -unsaturated carboxylic acids are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate , 2-Ethlyhexyl (meth) acrylate, octyl (meth) acrylate and lauryl (meth) acrylate.
  • n-butyl acrylate is used.
  • alkoxyalkyl esters of the ⁇ , ⁇ -unsaturated carboxylic acids are methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and methoxyethyl (meth) acrylate.
  • methoxyethyl acrylate is used.
  • Particularly preferred hydroxyalkyl esters of the ⁇ , ⁇ -unsaturated carboxylic acids are hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxy (butyl (meth) acrylate.
  • esters of the ⁇ , ⁇ -unsaturated carboxylic acids are, for example, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, epoxy (meth) acrylate and urethane (meth) acrylate.
  • monomers are vinylaromatics such as styrene, ⁇ -methylstyrene and vinylpyridine.
  • the proportions of conjugated diene and ⁇ , ⁇ -unsaturated nitrile in the nitrile rubbers according to the invention can vary within wide limits.
  • the proportion of or the sum of the conjugated dienes is usually in the range of 20 to 95 wt.%, Preferably in the range of 40 to 90 wt .-%, particularly preferably in the range of 60 to 85 wt.%, Based on the total polymer.
  • the proportion of or the sum of the ⁇ , ⁇ -unsaturated nitriles is usually from 5 to 80% by weight, preferably from 10 to 60% by weight, more preferably from 15 to 40% by weight, based on the total polymer.
  • the proportions of the monomers in each case add up to 100% by weight.
  • the additional monomers can be present in amounts of from 0 to 40% by weight, preferably from 0.1 to 40% by weight, particularly preferably from 1 to 30% by weight, based on the total polymer. In this case, corresponding proportions of the conjugated dienes and / or of the ⁇ , ⁇ -unsaturated nitriles are replaced by the proportions of these additional monomers, wherein the proportions of all monomers continue to add up to 100 wt .-%.
  • esters of (meth) acrylic acid are used as additional monomers, this usually takes place in amounts of from 1 to 25% by weight.
  • ⁇ , ⁇ -unsaturated mono- or dicarboxylic acids are used as additional monomers, this is usually carried out in amounts of less than 10% by weight.
  • the nitrogen content is determined in the nitrile rubbers according to the invention according to DIN 53 625 according to Kjeldahl. Due to the content of polar comonomers, the nitrile rubbers are usually soluble in methyl ethyl ketone at 20 ° C ⁇ 85 wt.%.
  • the nitrile rubbers have Mooney values (ML (1 + 4 @ 100 ° C.)) of from 10 to 150, preferably from 20 to 100 Mooney units, more preferably from 25 to 60 Mooney units. This is the value MV1 in the sense of the formula (I).
  • the glass transition temperatures of the nitrile rubbers are in the range -70 ° C to + 10 ° C, preferably in the range -60 ° C to 0 °
  • nitrile rubbers which have repeating units of acrylonitrile, 1,3-butadiene and optionally one or more further copolymerisable monomers.
  • nitrile rubbers the repeat units of acrylonitrile, 1,3-butadiene and one or more ⁇ , ⁇ -unsaturated mono- or dicarboxylic acid, their esters or amides, and in particular repeat units of an alkyl ester of an ⁇ , ⁇ -unsaturated carboxylic acids, very particularly preferably methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Octyl (meth) acrylate or lauryl (meth) acryl
  • the nitrile rubber according to the invention preferably comprises 2,2,4,6,6-pentamethylheptane-4-thio, 2,4,4,6,6-pentamethylheptane-2-thio, 2,3,4,6,6-pentamethyl heptane-2-thio and 2,3,4,6,6-pentamethylheptane-3-thio end groups.
  • the preparation of the nitrile rubbers takes place in the process according to the invention by emulsion polymerization.
  • emulsifiers water-soluble salts of anionic emulsifiers or neutral emulsifiers can be used.
  • Anionic emulsifiers are preferably used.
  • Modified resin acids obtained by dimerization, disproportionation, hydrogenation and modification of resin acid mixtures containing abietic acid, neoabietic acid, palustric acid, levopimaric acid can be used as anionic emulsifiers.
  • a particularly preferred modified rosin acid is the disproportionated rosin acid ( Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, Volume 31, pp. 345-355 ).
  • anionic emulsifiers and fatty acids can be used. These contain 6 to 22 C atoms per molecule. They can be fully saturated or contain one or more double bonds in the molecule.
  • fatty acids are caproic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid.
  • the carboxylic acids are usually based on origin-specific oils or fats such. Castoroil, cottonseed, peanut oil, linseed oil, coconut fat, palm kernel oil, olive oil, rapeseed oil, soybean oil, fish oil and beef tallow, etc. ( Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, Vol. 13, pp. 75-108 ).
  • Preferred carboxylic acids are derived from coconut fatty acid and beef tallow and are partially or completely hydrogenated.
  • Such carboxylic acids based on modified resin acids or fatty acids are used as water-soluble lithium sodium, potassium and ammonium salts.
  • the sodium and potassium salts are preferred.
  • Anionic emulsifiers are also sulfonates, sulfates and phosphates bonded to an organic radical.
  • Suitable organic radicals are aliphatic, aromatic, alkylated aromatics, fused aromatics, and methlyene-bridged aromatics, wherein the methylene-bridged and fused aromatics may additionally be alkylated.
  • the length of the alkyl chains is 6 to 25 C atoms.
  • the length of the alkyl chains bonded to the aromatics is between 3 and 12 C atoms.
  • the sulfates, sulfonates and phosphates are used as lithium, sodium, potassium and ammonium salts.
  • the sodium, potassium and ammonium salts are preferred.
  • sulfonates, sulfates and phosphates are Na lauryl sulfate, Na alkyl sulfonate, Na alkylarylsulfonate, Na salts methylenverbschreibter arylsulfonates, Na salts of alkylated naphthalenesulfonates and the Na salts of methlyenverbschreibter Napthalinsulfonate, also may be oligomerized, wherein the Otigimermaschinesgrad lies between 2 to 10.
  • the alkylated naphthalenesulfonic acids and the methylene-bridged (and optionally alkylated) naphthalenesulfonic acids are present as mixtures of isomers, which may also contain more than 1 sulfonic acid group (2 to 3 sulfonic acid groups) in the molecule.
  • Na lauryl sulfate Na alkylsulfonate mixtures having 12 to 18 C atoms
  • Na alkylaryl sulfonates Na diisobutylene naphthalene sulfonate, methylene-bridged polynaphthalene sulfonate mixtures and methylene-bridged aryl sulfonate mixtures.
  • Neutral emulsifiers are derived from addition products of ethylene oxide and propylene oxide on compounds with sufficiently acidic hydrogen. These include, for example, phenol, alkylated phenol and alkylated amines. The average degrees of polymerization of the epoxides are between 2 and 20. Examples of neutral emulsifiers are ethoxylated nonylphenols having 8, 10 and 12 ethylene oxide units. The neutral emulsifiers are usually not used alone, but in combination with anionic emulsifiers.
  • the emulsifiers are used in an amount of 0.2 to 15 parts by weight, preferably 0.5 to 12.5 parts by weight, particularly preferably 1.0 to 10 parts by weight, based on 100 parts by weight of the monomer mixture used.
  • the emulsion polymerization is carried out using the emulsifiers mentioned. If, after completion of the polymerization, latices are obtained which tend to premature self-coagulation due to a certain instability, the said emulsifiers can also be used for the post-stabilization of the latices. This may be necessary in particular before removal of unreacted monomers by treatment with water vapor and before latex storage.
  • the aforesaid mixture for controlling the molecular weight of the nitrile rubber is used in amounts of from 0.05 to 3 parts by weight, preferably from 0.1 to 1.5 parts by weight, based on 100 parts by weight of the monomer mixture.
  • the metering of the mixture for controlling the molecular weight is carried out either at the beginning of the polymerization or in portions during the polymerization, with the portionwise addition of all and also individual components of the regulator mixture during the polymerization being preferred.
  • the nitrile rubber in this case, 2,2,4,6,6-pentamethylheptane-4-thio, 2,4,4,6,6-pentamethylheptane-2-thio, 2,3,4,6,6 Pentamethylheptan-2-thio and 2,3,4,6,6-pentamethylheptane-3-thio end groups.
  • polymerization initiators which decompose into radicals. These include compounds containing one -OO unit (peroxo compounds) or one -N ⁇ N unit (azo compound).
  • the peroxo compounds include hydrogen peroxide, peroxodisulfates, peroxodiphosphates, hydroperoxides, peracids, peracid esters, peracid anhydrides and peroxides having two organic radicals.
  • hydroperoxides e.g. t-butyl hydroperoxide, cumene hydroperoxide and p-menthane hydroperoxide.
  • Suitable peroxides having two organic radicals are dibenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl perbenzoate, t-butyl peracetate, etc.
  • Suitable azo compounds are azobisisobutyronitrile, azobisvaleronitrile and azobiscyclohexanenitrile.
  • Hydrogen peroxide, hydroperoxides, peracids, peracid esters, peroxodisulfate and peroxodiphosphate are also used in combination with reducing agents.
  • Suitable reducing agents are sulfenates, sulfinates, sulfoxylates, dithionite, sulfite, metabisulfite, disulfite, sugars, urea, thiourea, xanthates, thioxanthogenates, hydrazinium salts, amines and amine derivatives such as aniline, dimethylaniline, monoethanolamine, diethanolamine or triethanolamine.
  • Initiator systems consisting of an oxidizing and a reducing agent are called redox systems.
  • salts of transition metal compounds such as iron, cobalt or nickel in combination with suitable complexing agents such as sodium ethylenediamtetraacetat, sodium nitrilotriacetate and trisodium phosphate or Tetrakaliumdiphsophat.
  • Preferred redox systems are, for example: 1) potassium peroxodisulfate in combination with triethanolamine, 2) ammonium peroxodiphosphate in combination with sodium metabisulfite (Na 2 S 2 O 5 ), 3) p-menthane hydroperoxide / sodium formaldehyde sulfoxylate in combination with Fe-II sulfate (FeSO 4 .7H 2 O), sodium ethylenediaminoacetate and trisodium phosphate; 4) cumene hydroperoxide / sodium formaldehyde sulfoxylate in combination with Fe-II sulfate (FeSO 4 .7H 2 O), sodium ethylenediaminoacetate and tetrapotassium diphosphate.
  • the amount of oxidizing agent is 0.001 to 1 part by weight based on 100 parts by weight of monomer.
  • the molar amount of reducing agent is between 50% to 500% based on the molar amount of the oxidizing agent used.
  • the molar amount of complexing agent refers to the amount of transition metal used and is usually equimolar with this.
  • reaction rate can be controlled.
  • the polymerization time is in the range of 5 h to 15 h and depends essentially on the acrylonitrile content of the monomer mixture and on the polymerization temperature.
  • the polymerization temperature is in the range of 0 to 30 ° C, preferably in the range of 5 to 25 ° C.
  • a stopper is added to the reaction mixture.
  • Suitable for this purpose are, for example, dimethyldithiocarbamate, Na nitrite, mixtures of dimethyldithiocarbamate and Na nitrite, hydrazine and hydroxylamine, and salts derived therefrom, such as hydrazinium sulfate and hydroxylammonium sulfate, diethylhydroxylamine, diisopropylhydroxylamine, water-soluble salts of Hydroquinone, sodium dithionite, phenyl- ⁇ -naphthylamine and aromatic phenols such as tert-butyl catechol, or phenothiazine.
  • the amount of water used in the emulsion polymerization is in the range of 100 to 900 parts by weight, preferably in the range of 120 to 500 parts by weight, more preferably in the range of 150 to 400 parts by weight of water based on 100 parts by weight the monomer mixture.
  • salts may be added to the aqueous phase to reduce the viscosity during the polymerization, for pH adjustment as well as for pH buffering.
  • salts of monovalent metals in the form of potassium and sodium hydroxide, sodium sulfate, sodium carbonate, sodium bicarbonate, lithium chloride, sodium chloride and potassium chloride.
  • the amounts of these electrolytes are in the range 0 to 1 parts by weight, preferably 0 to 0.5 parts by weight based on 100 parts by weight of the monomer mixture.
  • the addition of a chloride-containing salt during the emulsion polymerization is necessary if neither in the subsequent coagulation nor in the subsequent washing of the coagulated nitrile rubber, a chloride-containing salt is to be used (feature (iv) of the inventive method).
  • the polymerization can be carried out either batchwise or continuously in a stirred tank cascade.
  • the polymerization is started with 10 to 80% by weight, preferably 30-50% by weight, of the total amount of initiator.
  • the addition of individual components of the initiator system is possible.
  • acrylonitrile or butadiene are postdosed, if the composition is outside the azeotropic butadiene / acrylonitrile ratio.
  • the replenishment takes place - as in the DD 154 702 indicated - preferably computer-controlled on the basis of a computer program.
  • a post-stabilization of the latex with emulsifier can take place.
  • the abovementioned emulsifiers in amounts of 0.1 to 2.5% by weight, preferably 0.5 to 2.0% by weight. % based on 100 parts by weight of nitrile rubber.
  • one or more anti- aging agents can be added to the latex.
  • phenolic, aminic and other anti-aging agents are suitable.
  • Suitable phenolic antioxidants are alkylated phenols, styrenated phenol, hindered phenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol (BHT), 2,6-di-tert. Butyl-4-ethylphenol, sterically hindered phenols containing ester groups, thioether-containing sterically hindered phenols, 2,2'-methylenebis (4-methyl-6-tert-butylphenol) (BPH) and sterically hindered thiobisphenols.
  • BHT 2,6-di-tert-butylphenol
  • BHT 2,6-di-tert-butyl-p-cresol
  • Butyl-4-ethylphenol sterically hindered phenols containing ester groups
  • thioether-containing sterically hindered phenols 2,2'-methylenebis (4-methyl-6-tert-but
  • a discoloration of the rubber is of no importance, also aminic aging inhibitor z.
  • B mixtures of diaryl-p-phenylenediamines (DTPD), octylated diphenylamine (ODPA), phenyl- ⁇ -naphthylamine (PAN), phenyl- ⁇ -naphthylamine (PBN), preferably those based on phenylenediamine used.
  • DTPD diaryl-p-phenylenediamines
  • ODPA octylated diphenylamine
  • PAN phenyl- ⁇ -naphthylamine
  • PBN phenyl- ⁇ -naphthylamine
  • phenylenediamines are N-isopropyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine (6PPD), N-1,4-dimethylpentyl-N'-phenylphenyl Phenylenediamine (7PPD), N, N'-bis-1,4- (1,4-dimethylpentyl) -p-phenylenediamine (77PD), etc.
  • anti-aging agents include phosphites such as tris (nonylphenyl) phosphite, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), 2-mercaptobenzimidazole (MBI), methyl 2-mercaptobenzimidazole (MMBI), zinc methylmercaptobenzimidazole ( ZMMBI).
  • TMQ 2,2,4-trimethyl-1,2-dihydroquinoline
  • MBI 2-mercaptobenzimidazole
  • MMBI methyl 2-mercaptobenzimidazole
  • ZMMBI zinc methylmercaptobenzimidazole
  • TMQ, MBI and MMBI are mainly used for NBR grades that are vulcanized peroxide.
  • the latex is used with a pH of at least 6, preferably of> 6.
  • this pH is adjusted by addition of a base, preferably of ammonia or sodium or potassium hydroxide.
  • the coagulation is carried out using at least one salt selected from the group consisting of aluminum, calcium, magnesium, sodium, potassium and lithium salts.
  • halide more preferably chloride, nitrate, sulfate, bicarbonate, carbonate, formate and acetate.
  • Suitable examples are sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium nitrate, potassium nitrate, sodium sulfate, potassium sulfate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, aluminum sulfate, potassium aluminum sulfate (potassium alum), sodium aluminum sulfate (sodium alum), sodium acetate, calcium acetate and calcium formate.
  • the specific calcium content of the nitrile rubbers according to the invention is that either at least one water-soluble calcium salt is present in the latex coagulation or - if this is not the case - the subsequent washing of the coagulated nitrile rubber using non-deionized and thus calcium ion-containing water is carried out.
  • calcium chloride is preferred.
  • the concentration of the solution of one or more salts selected from the group consisting of aluminum, calcium, magnesium, sodium, potassium and lithium salts is 3 to 30 wt.%.
  • water containing Ca ions is preferably used.
  • the total amount of salts necessary for the latex coagulation selected from the group consisting of aluminum, calcium, magnesium, sodium, potassium and lithium salts is 0.5-200% by weight, preferably 0.8-80% by weight. %, more preferably 1-50% by weight of salt, based on 100 parts by weight of nitrile rubber.
  • precipitants may also be used in the coagulation.
  • Suitable precipitation aids are, for example, water-soluble polymers. These are nonionic, anionic or cationic.
  • nonionic polymeric precipitation aids are modified cellulose such as hydroxyalkyl cellulose or methyl cellulose and adducts of ethylene oxide and propylene oxide on compounds with acidic hydrogen.
  • compounds with acidic hydrogen are: Fatty acid, sugars such as sorbitol, mono- and di-fatty acid glycerides, phenol, alkylated phenols, (alkyl) phenol / formaldehyde condensates, etc.
  • the addition products of ethylene oxide and propylene oxide to these compounds may be random and block-like. Of these products, those in which solubility decreases with increasing temperature are preferred. Characteristic turbidity temperatures are in the range 0 to 100 ° C, in particular in the range of 20 to 70 ° C.
  • anionic polymeric precipitation aids are the homopolymers and copolymers of (meth) acrylic acid, maleic acid, maleic anhydride, etc.
  • the sodium salt of polyacrylic acid is preferred.
  • Cationic polymeric precipitation aids are usually based on polyamines and on homo- and copolymers of (meth) acrylamide. Preference is given to polymethacxrylamides and polyamines, in particular based on epichlorohydrin and dimethylamine.
  • the amounts of polymeric precipitation aids are 0.01 to 5 parts by weight, preferably 0.05 to 2.5 parts by weight per 100 parts by weight of nitrile rubber.
  • the latex used for coagulation has expediently a solids concentration in the range of 1% to 40%, preferably in the range of 5% to 35% and particularly preferably in the range of 15 to 30% by weight.
  • the latex coagulation is carried out in the temperature range from 10 to 100 ° C. Preferably, the latex coagulation is carried out at a temperature of 20 to 90 ° C.
  • the latex coagulation can be continuous or discontinuous, preferably continuous.
  • the nitrile rubber is usually present in the form of so-called crumbs.
  • the laundry of the coagulated NBR is therefore also referred to as crumb laundry.
  • deionized water also referred to as "DW”
  • BW Deionized water
  • the washing of the coagulated nitrile rubber should be carried out using non-deionized and therefore calcium ion-containing water.
  • the wash is stirred at a temperature in the range of 15 to 90 ° C, preferably at a temperature in the range of 20 to 80 ° C.
  • the amount of washing water is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, and more preferably 1 to 5 parts by weight, based on 100 parts by weight of nitrile rubber.
  • the rubber crumbs are subjected to a multi-stage washing, wherein the rubber crumbs are partially dewatered between the individual washing stages.
  • the residual moistures of the crumbs between the individual washing stages are in the range from 5 to 50% by weight, preferably in the range from 7 to 25% by weight.
  • the number of washing stages is usually from 1 to 7, preferably from 1 to 3.
  • the washing is carried out batchwise or continuously. Preference is given to using a multistage, continuous process, with countercurrent washing being preferred for the careful handling of water.
  • the adjustment of the cation contents remaining in the nitrile rubber may additionally and if desired be influenced by the degree of mechanical pre-dewatering. This is particularly appropriate when a so-called inefficient laundry is applied. Efficient laundry already provides the appropriate cation levels.
  • the water contents after the mechanical pre-dewatering are in the range of 5 to 25 wt.%.
  • the water contents after mechanical pre-dewatering are 5 to 15% by weight, in particular 5 to 10% by weight.
  • the drying of the pre-dehydrated nitrile rubber takes place in a fluid bed dryer or in a plate dryer.
  • the drying temperatures are between 80 and 150 ° C. Preference is given to drying with a temperature program, the temperature being lowered towards the end of the drying process.
  • the nitrile rubbers according to the invention which have the specified content of calcium and chlorine, have the desired high storage stability LS of a maximum of 5 Mooney units.
  • the high storage stability already has positive effects during the drying of the nitrile rubber, since otherwise a certain aging of the rubber takes place involuntarily during this drying.
  • the high storage stability facilitates the setting of a given target Mooney viscosity. This reduces the amount of non-conforming nitrile rubber.
  • the high storage stability results in a reduction of the complaints that result from changing the Mooney viscosity during long storage or transport times.
  • the rubbers according to the invention are suitable for the reproducible production of vulcanizable mixtures.
  • the molded parts obtainable therefrom by vulcanization are thus also distinguished by a reproducible mechanical and physical property profile.
  • the invention therefore also relates to the use of the nitrile rubbers according to the invention for the production of vulcanizable mixtures containing at least one nitrile rubber according to the invention, at least one crosslinker and optionally further additives.
  • vulcanizable mixtures are prepared by mixing at least one nitrile rubber according to the invention, at least one crosslinker and optionally further additives.
  • Suitable crosslinkers are, for example, peroxidic crosslinkers such as bis (2,4-dichlorobenzyl) peroxide, dibenzoyl peroxide, bis (4-chlorobenzoyl) peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcylohexane, tert Butyl perbenzoate, 2,2-bis (t-butylperoxy) butene, 4,4-di-tert-butyl peroxynonylvalerate, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, tert-butylcumyl peroxide, 1,3-bis (t-butylperoxy isopropyl) benzene, di-t-butyl peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) hexyn-3.
  • crosslinking yield can be increased.
  • triallylisocyanurate triallylcyanurate, triallylcyanurate, trimethylolpropane tri (meth) acrylate, triallyltrimellithate, Ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane trimethacrylate, Zn diacrylate, Zn dimethacrylate, 1,2-polybutadiene or N, N'-m-phenylenedimaleimide.
  • the total amount of crosslinker (s) is usually in the range of 1 to 20 phr, preferably in the range of 1.5 to 15 phr and more preferably in the range of 2 to 10 phr, based on the nitrile rubber.
  • crosslinkers it is also possible to use sulfur in elementary soluble or insoluble form or sulfur donors.
  • Suitable sulfur donors are, for example, dimorpholyl disulfide (DTDM), 2-morpholinodithiobenzothiazole (MBSS), caprolactam disulfide, dipentamethylene thiuram tetrasulfide (DPTT), and tetramethylthiuram disulfide (TMTD).
  • DTDM dimorpholyl disulfide
  • MBSS 2-morpholinodithiobenzothiazole
  • caprolactam disulfide caprolactam disulfide
  • DPTT dipentamethylene thiuram tetrasulfide
  • TMTD tetramethylthiuram disulfide
  • crosslinking of the nitrile rubbers according to the invention can also be carried out only in the presence of the abovementioned additives, i. without the addition of elemental sulfur or sulfur donors.
  • additives with the aid of which the crosslinking yield can be increased e.g. Dithiocarbamates, thiurams, thiazoles, sulfenamides, xanthogenates, guanidine derivatives, caprolactams and thiourea derivatives.
  • dithiocarbamates can be used, for example: ammonium dimethyldithiocarbamate, sodium diethyldithiocarbamate (SDEC), Natriumdibutyl-dithiocarbamate (SDBC), zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), Zinkdibutyldithio-carbamate (ZDBC), zinc ethylphenyldithiocarbamate (ZEPC), zinc dibenzyldithiocarbamate (ZBEC), zinc pentamethylenedithiocarbamate ( Z5MC), tellurium diethyldithio-carbamate, nickel dibutyldithiocarbamate, nickel dimethyldithiocarbamate and zinc diisononyldithio-carbamate.
  • SDEC sodium diethyldithiocarbamate
  • SDBC Natriumdibutyl-dithi
  • thiurams there may be used, for example, tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), dimethyldiphenylthiuram disulfide, tetrabenzylthiuram disulfide, dipentamethylenethiuram tetrasulfide and tetraethylthiuram disulfide (TETD).
  • thiazoles there may be used, for example, 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), zinc mercaptobenzothiazole (ZMBT) and copper 2-mercaptobenzothiazole.
  • sulfenamide derivatives which can be used are: N-cyclohexyl-2-benzothiazyl sulfenamide (CBS), N-tert-butyl-2-benzthiazyl sulfenamide (TBBS), N, N'-dicyclohexyl-2-benzthiazyl sulfenamide (DCBS), 2-morpholinothiobenzothiazole (MBS), N-Oxydiethylenethiocarbamyl-N-tert-butylsulfenamide and Oxydiethylenethiocarbamyl-N-oxyethylene-sulfenamide.
  • CBS N-cyclohexyl-2-benzothiazyl sulfenamide
  • TBBS N-tert-butyl-2-benzthiazyl sulfenamide
  • DCBS N'-dicyclohexyl-2-benzthiazyl sulfenamide
  • MFS 2-morpholinothiobenzothiazo
  • xanthates there may be used, for example, sodium dibutylxanthogenate, zinc isopropyldibutylxanthogenate and zinc dibutylxanthogenate.
  • guanidine derivatives can be used, for example: diphenylguanidine (DPG), di-o-tolylguanidine (DOTG) and o-tolylbiguanide (OTBG).
  • DPG diphenylguanidine
  • DDG di-o-tolylguanidine
  • OTBG o-tolylbiguanide
  • dithiophosphates which can be used are: zinc dialkydithiophosphates (chain length of the alkyl radicals C 2 to C 16 ), copper dialkyldithiophosphates (chain length of the alkyl radicals C 2 to C 16 ) and dithiophosphoryl polysulfide.
  • caprolactam for example, dithio-bis-caprolactam can be used.
  • thiourea derivatives for example, N, N'-diphenylthiourea (DPTU), diethylthiourea (DETU) and ethylene thiourea (ETU) can be used.
  • DPTU N, N'-diphenylthiourea
  • DETU diethylthiourea
  • ETU ethylene thiourea
  • additives are, for example: zinc diamine diisocyanate, hexamethylenetetramine, 1,3-bis (citraconimidomethyl) benzene and cyclic disulfanes.
  • the additives mentioned as well as the crosslinking agents can be used both individually and in mixtures.
  • the following substances for crosslinking the nitrile rubbers are preferably used: sulfur, 2-mercaptobenzothiazole, tetramethylthiuram disulfide, tetramethylthiuram monosulfide, zinc dibenzyldithiocarbamate, dipentamethylenethiuram tetrasulfide, Zinkdialkydithiophosphat, dimorpholyl, tellurium diethyldithiocarbamate, nickel dibutyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dimethyldithiocarbamate and dithio-bis-caprolactam.
  • crosslinking agents and aforementioned additives can each be used in amounts of about 0.05 to 10 phr, preferably 0.1 to 8 phr, in particular 0.5 to 5 phr (single dose, in each case based on the active substance).
  • sulfur crosslinking in addition to the crosslinking agents and the abovementioned additives, further inorganic or organic substances, for example: zinc oxide, zinc carbonate, lead oxide, magnesium oxide, saturated or unsaturated organic fatty acids and their zinc salts, polyalcohols, Amino alcohols such as triethanolamine and amines such as dibutylamine, dicyclohexylamine, cyclohexylethylamine and polyetheramines.
  • further inorganic or organic substances for example: zinc oxide, zinc carbonate, lead oxide, magnesium oxide, saturated or unsaturated organic fatty acids and their zinc salts, polyalcohols, Amino alcohols such as triethanolamine and amines such as dibutylamine, dicyclohexylamine, cyclohexylethylamine and polyetheramines.
  • scorch retarders can also be used. These include cyclohexylthiophthalimide (CTP), N, N'-dinitrosopentamethylenetetramine (DNPT), phthalic anhydride (PTA) and diphenylnitrosamine. Cyclohexylthiophtalimide (CTP) is preferred.
  • the nitrile rubber of the invention may also be mixed with other customary rubber additives.
  • fillers include, for example, typical and well-known substances such as fillers, filler activators, antiozonants, antiaging agents, antioxidants, processing aids, extender oils, plasticizers, reinforcing materials and mold release agents.
  • fillers for example, carbon black, silica, barium sulfate, titanium dioxide, zinc oxide, calcium oxide, calcium carbonate, magnesium oxide, alumina, iron oxide, aluminum hydroxide, magnesium hydroxide, aluminum silicates, diatomaceous earth, talc, kaolins, bentonites, carbon nanotubes, Teflon (the latter preferably in powder form), or Silicates are used.
  • Suitable filler activators are, in particular, organic silanes, for example vinyltrimethyloxysilane, vinyldimethoxymethylsilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N-cyclohexyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane Hexadecyltrimethoxysilane or (octadecyl) methyldimethoxysilane into consideration.
  • organic silanes for example vinyltrimethyloxysilane, vinyldimethoxymethylsilane, vinyltriethoxysilane, vinyltris (2-me
  • filler activators are, for example, surfactants such as triethanolamine and ethylene glycols having molecular weights of 74 to 10,000 g / mol.
  • the amount of filler activators is usually 0 to 10 phr based on 100 phr of the nitrile rubber.
  • anti-aging agents it is possible to add to the vulcanizable mixtures those already described in connection with the latex coagulation in this application.
  • she are usually used in amounts of about 0 to 5 phr, preferably 0.5 to 3 phr, based on 100 phr of the nitrile rubber.
  • Suitable mold release agents are, for example: saturated and partially unsaturated fatty and oleic acids and derivatives thereof (fatty acid esters, fatty acid salts, fatty alcohols, fatty acid amides) which are preferably used as a mixing component, furthermore products which can be applied to the mold surface, for example products based on low molecular weight silicone compounds , Products based on fluoropolymers and products based on phenolic resins.
  • the mold release agents are used as a blend component in amounts of about 0 to 10 phr, preferably 0.5 to 5 phr, based on 100 phr of the nitrile rubber.
  • fibers made of glass, according to the doctrine of US Patent No. 4,826,721 is possible as well as the reinforcement by cords, fabrics, fibers of aliphatic and aromatic polyamides (Nylon®, Aramid®), polyesters and natural fiber products.
  • the invention further provides a process for the production of moldings based on at least one nitrile rubber according to the invention, which comprises vulcanizing the vulcanizable mixture described above in a molding process, preferably using an injection molding process.
  • the invention thus also relates to the special molding which is obtainable by the aforementioned vulcanization process.
  • a plurality of moldings can be made, e.g. a gasket, cap, tube or membrane.
  • the nitrile rubbers according to the invention with the specific ion characteristic for producing an O-ring seal, a gasket, a shaft seal, a sealing collar, a sealing cap, a dust cap, a plug seal, a Thermoisolierschlauchs (with and without PVC additive), an oil cooler hose, one Air intake hose, a power steering hose or a pump diaphragm.
  • the metathesis is * WO-A-02/100941 as well as the WO-A-02/100905 known.
  • Hydrogenation can be carried out using homogeneous or heterogeneous hydrogenation catalysts. It is also possible to carry out the hydrogenation in situ, i. in the same reaction vessel in which optionally before the metathesis degradation was carried out and without need to isolate the degraded nitrile rubber. The hydrogenation catalyst is simply added to the reaction vessel.
  • the catalysts used are usually based on rhodium, ruthenium or titanium, but it is also possible to use platinum, iridium, palladium, rhenium, ruthenium, osmium, cobalt or copper either as metal or preferably in the form of metal compounds (see, for example, US Pat US-A-3,700,637 . DE-A-25 39 132 . EP-A-0 134 023 . DE-OS 35 41 689 . DE-OS 35 40 918 . EP-A-0 298 386 . DE-OS 35 29 252 . DE-OS 34 33 392 . US-A-4,464,515 and US-A-4,503,196 ).
  • the selective hydrogenation can be achieved, for example, in the presence of a rhodium- or ruthenium-containing catalyst. It is possible, for example, to use a catalyst of the general formula (R 1 m B) 1 MX n , wherein M is ruthenium or rhodium, R 1 are the same or different and represent a C 1 -C 8 alkyl group, a C 4 -C 8 cycloalkyl group, a C 6 -C 15 aryl group or a C 7 -C 15 aralkyl group.
  • X is hydrogen or an anion, preferably halogen and more preferably chlorine or bromine
  • 1 is 2,3 or 4
  • m is 2 or 3
  • n is 1, 2 or 3, preferably 1 or 3.
  • Preferred catalysts are tris (triphenylphosphine) rhodium (I) chloride, tris (triphenylphosphine) rhodium (III) chloride and tris (dimethyl sulfoxide) rhodium (III) chloride and tetrakis ( triphenylphosphine) rhodium hydride of the formula (C 6 H 5 ) 3 P) 4 RhH and the corresponding compounds in which the triphenylphosphine has been wholly or partly replaced by tricyclohexylphosphine.
  • the catalyst can be used in small quantities. An amount in the range of 0.01-1% by weight, preferably in the range of 0.03-0.5% by weight, and more preferably in the range of 0.1-0.3% by weight based on the weight of the polymer are suitable.
  • co-catalyst which is a ligand of the formula R 1 m B, where R 1 , m and B have the meanings given above for the catalyst.
  • R 1 , m and B have the meanings given above for the catalyst.
  • m is 3
  • B is phosphorus and the radicals R 1 may be the same or different.
  • co-catalysts with trialkyl, tricycloalkyl, Triaryl, triaralkyl, diaryl-monoalkyl, diaryl-monocycloalkyl, dialkyl-monoaryl, dialkylmonocycloalkyl, dicycloalkyl-monoaryl or dicyclalkyl-monoaryl-radicals.
  • co-catalysts can be found, for example, in US-A-4,631,315 , Preferred co-catalyst is triphenylphosphine.
  • the co-catalyst is preferably used in amounts in a range of 0.3-5 wt.%, Preferably in the range of 0.5-4 wt.%, Based on the weight of the nitrile rubber to be hydrogenated.
  • the weight ratio of the rhodium-containing catalyst to the cocatalyst is preferably in the range from 1: 3 to 1:55, particularly preferably in the range from 1: 5 to 1:45.
  • the co-catalyst Based on 100 parts by weight of the nitrile rubber to be hydrogenated, suitably 0.1 to 33 parts by weight of the co-catalyst, preferably 0.5 to 20 and most preferably 1 to 5 parts by weight, especially more than 2 but less than 5 parts by weight of co-catalyst based 100 parts by weight of the nitrile rubber to be hydrogenated.
  • hydrogenation is understood as meaning a conversion of the double bonds present in the starting nitrile rubber to at least 50%, preferably 70-100%, particularly preferably 80-100%.
  • heterogeneous catalysts are usually supported catalysts based on palladium, z. B. supported on carbon, silica, calcium carbonate or barium sulfate.
  • the optionally hydrogenated nitrile rubbers obtained after the metathesis and / or hydrogenation reaction of the nitrile rubbers according to the invention can be introduced into vulcanizable compositions analogously to the nitrile rubbers of the invention and used for the production of vulcanizates and moldings based on such vulcanizates.
  • These optionally hydrogenated nitrile rubbers have Mooney viscosities (ML (1 + 4 @ 100 ° C)) of from 1 to 50, preferably from 1 to 40 Mooney units.
  • NBR latexes A, B and C used in Examples 1) to 5) was carried out according to the base formulation given in Table 1, wherein all starting materials are stated in parts by weight based on 100 parts by weight of the monomer mixture.
  • Table 1 also lists the respective polymerization conditions ⁇ b> ⁇ u> Table 1: ⁇ / u> ⁇ /b> Latex no.
  • the preparation of the NBR latex was carried out batchwise in a 2 m 3 autoclave with stirrer.
  • the autoclave batches each used 350 kg of the monomer mixture and a total amount of water of 700 kg. From this amount of water, 650 kg with the emulsifiers (Erkantol ® BXG, Baykanol ® PQ and K salt of coconut fatty acid) and sodium hydroxide in an autoclave and rinsed with a stream of nitrogen. Thereafter, the destabilized monomers and the first indicated in Table 1 subset of the molecular weight regulator t-DDM were added and the reactor sealed.
  • the emulsifiers Erkantol ® BXG, Baykanol ® PQ and K salt of coconut fatty acid
  • latex B the addition of a total of 19 parts by weight of acrylonitrile was staggered: 12.5 parts by weight of acrylonitrile were initially charged in the reactor, and a further 6.5 parts by weight were metered in at a conversion of 35%.
  • the addition of the t-DDM was also graded for latex B: 0.27 parts by weight of t-DDM were introduced into the reactor, 0.15 parts by weight were metered in at 20% conversion and 0.06 parts by weight were post-dosed at 40% conversion.
  • t-DDM t-DDM
  • 0.5 part by weight of t-DDM was introduced into the reactor, and 0.2 part by weight was replenished at 15% conversion.
  • the rubber latices or solid rubbers obtained had the following properties: Latex no. A B C Particle diameter (d50) [nm] 400 360 350 Solids content [% by weight] 20.5 22.8 24.8 PH value 8.4 11.4 10.9 Acrylonitrile content [wt. %] 28.9 18.8 38.6
  • Vulkanox ® KB 1.25% Vulkanox ® KB wt. Based on NBR solid
  • Vulkanox.RTM ® -KB dispersion was prepared beforehand at 95-98 ° C by means of an Ultraturrax and comprised: 360 g Deionized water ("DW water”) 40 g Ethoxylated nonylphenol (NP10 from Lanxess GmbH) 400 g Vulkanox.RTM ® KB
  • Variation of latex coagulation and crumb wash conditions was discontinuous on aliquots of latices A, B and C in a 100 liter stirrable, open container.
  • the container had an inflow and outflow.
  • two rails were attached, so that the drainage could be shut off by means of a sieve (mesh size 2 mm) before carrying out the laundry, so the coagulated crumbs were not flushed out during the laundry.
  • the washing was carried out in the experiments described here with a constant water flow rate of 200 l / h.
  • deionized (DW) and non-deionized (BW) water was used.
  • the resulting in the precipitation latex serum was not before the laundry from the Coagulation tank removed; ie the latex serum was removed by dilution washing.
  • the framework conditions used for crumb washing (type of water, washing temperature, washing time, etc.) are listed in the following tables.
  • the rubber crumbs were removed with a sieve, pre-dewatered in a Welding screw to a residual moisture of 5 to 20 wt.% And dried discontinuously in a circulating air dryer to a residual moisture content of ⁇ 0, 6%.
  • the dried NBR rubbers were characterized by the Mooney viscosity before and after hot air storage for 48 hours at 100 ° C, i. the Mooney viscosity was determined once just after drying (i.e., before hot air storage) and then after 48 hours of hot melt aging at 100 ° C.
  • the calcium content was determined by inductively coupled plasma-optical emission spectrometry (OES) at a wavelength of 317.933 nm against acid matrix matched calibration solutions.
  • OES inductively coupled plasma-optical emission spectrometry
  • concentrations of the sample solutions for the respective wavelengths used were adapted to the linear range of the calibration ( B. Welz "Atomic Absorption Spectrometry", 2nd ed., Verlag Chemie, Weinheim 1985 )
  • the chlorine content of the nitrile rubbers according to the invention is determined as follows on the basis of DIN EN 14582, method A.
  • the nitrile rubber sample is digested in a pressure vessel according to Parr in a melt of sodium peroxide and potassium nitrate. Sulfite solution is added to the resulting melt and acidified with sulfuric acid. In the solution thus obtained, the resulting chloride is determined by potentiometric titration with silver nitrate solution and calculated as chlorine.
  • the crumb wash was in all cases at 20 ° C and with deionized water (DW).
  • the comparative examples are identified by a "V" before the numbering.
  • example Latex coagulation Washing time [H] Chlorine content [ppm] Ca [ppm] mg [ppm] ML (1 + 4 @ 100 ° C).
  • the crumb wash was in all cases at 20 ° C and either with deionized water (DW) or calcium ion-containing water (BW) example Latex coagulation washing conditions ML1 + 4 @ 100 ° C [ME] pH of the latex type of salt Conc. Of saline solution [Wt.%] Amount of salt bez.
  • DW deionized water
  • BW calcium ion-containing water
  • the Krümelskyskysche was carried out in all cases with calcium ion-containing water (BW).
  • BW calcium ion-containing water
  • the Krümelskyskysche was carried out in all cases with calcium ion-containing water (BW) example Latex coagulation washing conditions Chlorine content [ppm] Ca [ppm] ML 1 + 4 @ 100 ° C [ME] pH of the latex type of salt Conc. Of saline solution [Wt.%] Amount of salt bez. on NBR [Wt.
  • Example 36 (Inventive example)

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Claims (24)

  1. Caoutchouc nitrile, qui contient des unités de répétition d'au moins un nitrile α,β-insaturé, d'au moins un diène conjugué et éventuellement d'un ou de plusieurs autres monomères copolymérisables, et qui
    (i) présente une teneur en calcium d'au moins 150 ppm, par rapport au caoutchouc nitrile, et une teneur en chlore d'au moins 40 ppm, par rapport au caoutchouc nitrile, et
    (ii) contient des groupes terminaux 2,2,4,6,6-pentaméthylheptane-4-thio et/ou 2,4,4,6,6-pentaméthylheptane-2-thio et/ou 2,3,4,6,6-pentaméthylheptane-2-thio et/ou 2,3,4,6,6-pentaméthylheptane-3-thio.
  2. Caoutchouc nitrile selon la revendication 1, qui présente une teneur en calcium d'au moins 200 ppm, de préférence d'au moins 400 ppm, de manière particulièrement préférée de plus de 500 ppm, notamment d'au moins 600 ppm et de manière particulièrement préférée d'au moins 800 ppm de calcium, par rapport au caoutchouc nitrile.
  3. Caoutchouc nitrile selon la revendication 1 ou 2, qui présente une stabilité au stockage LS d'au plus 5 unités Mooney, de préférence de moins de 5 unités Mooney et de manière particulièrement préférée d'au plus 4 unités Mooney, la stabilité au stockage LS étant donnée par la formule (I) suivante : LS = MV ⁢ 2 - MV ⁢ 1
    Figure imgb0005
    dans laquelle
    MV1 représente la valeur de la viscosité de Mooney du caoutchouc nitrile et
    MV2 représente la valeur de la viscosité de Mooney du même caoutchouc nitrile après un stockage de 48 heures à 100 °C.
  4. Caoutchouc nitrile selon une ou plusieurs des revendications 1 à 3, qui contient des unités de répétition d'acrylonitrile, de 1,3-butadiène et éventuellement d'un ou de plusieurs autres monomères copolymérisables.
  5. Caoutchouc nitrile selon la revendication 4, qui comporte des unités de répétition d'un ou de plusieurs acides mono- ou dicarboxyliques α,β-insaturés, leurs esters ou amides, de préférence des unités de répétition d'un ester alkylique d'un acide carboxylique α,β-insaturé, notamment de (méth)acrylate de méthyle, de (méth)acrylate d'éthyle, de (méth)acrylate de propyle, de (méth)acrylate de n-butyle, de (méth)acrylate de t-butyle, de (méth)acrylate d'hexyle, de (méth)acrylate de 2-éthylhexyle, de (méth)acrylate d'octyle ou de (méth)acrylate de lauryle.
  6. Caoutchouc nitrile selon une ou plusieurs des revendications 1 à 5, qui présente une viscosité de Mooney MV1 (ML (1+4 @ 100 °C)) de 10 à 150, de préférence de 20 à 100 unités Mooney.
  7. Caoutchouc nitrile selon une ou plusieurs des revendications 1 à 6, ayant une température de transition vitreuse dans la plage allant de -70 °C à +10 °C, de préférence dans la plage allant de -60 °C à 0 °C.
  8. Caoutchouc nitrile selon une ou plusieurs des revendications 1 à 7, qui comporte des groupes terminaux 2,2,4,6,6-pentaméthylheptane-4-thio, 2,4,4,6,6-pentaméthylheptane-2-thio, 2,3,4,6,6-pentaméthylheptane-2-thio et 2,3,4,6,6-pentaméthylheptane-3-thio.
  9. Procédé de fabrication d'un caoutchouc nitrile selon une ou plusieurs des revendications 1 à 8 par polymérisation en émulsion d'au moins un nitrile α,β-insaturé, d'au moins un diène conjugué et éventuellement d'un ou de plusieurs autres monomères copolymérisables, le latex contenant le caoutchouc nitrile qui se forme tout d'abord lors de la polymérisation étant soumis à une coagulation et le caoutchouc nitrile coagulé étant ensuite lavé, caractérisé en ce que
    (i) la polymérisation en émulsion est réalisée en présence d'un mélange contenant du 2,2,4,6,6-pentaméthylheptanethiol-4, du 2,4,4,6,6-pentaméthylheptanethiol-2, du 2,3,4,6,6-pentaméthylheptanethiol-2 et du 2,3,4,6,6-pentaméthylheptanethiol-3,
    (ii) le latex contenant le caoutchouc nitrile qui se forme par la polymérisation est soumis à une coagulation en utilisant au moins un sel choisi dans le groupe constitué par les sels d'aluminium, de calcium, de magnésium, de sodium, de potassium et de lithium,
    (iii) un sel de calcium soluble dans l'eau est présent lors de la coagulation et/ou le lavage du caoutchouc nitrile coagulé est réalisé avec de l'eau contenant des ions calcium et
    (iv) un sel à base d'un chlorure est présent lors de la polymérisation en émulsion, lors de la coagulation ou lors du lavage ultérieur du caoutchouc nitrile coagulé.
  10. Procédé selon la revendication 9, dans lequel la polymérisation en émulsion est réalisée de manière discontinue ou continue dans une cascade de cuves agitées.
  11. Procédé selon la revendication 9 ou 10, dans lequel un ou plusieurs agents antivieillissement, de préférence agents antivieillissement phénoliques, sont ajoutés au latex contenant le caoutchouc nitrile avant ou pendant la coagulation.
  12. Procédé selon une ou plusieurs des revendications 9 à 11, dans lequel du chlorure de sodium, du chlorure de potassium, du chlorure de calcium, du chlorure de magnésium, du nitrate de sodium, du nitrate de potassium, du sulfate de sodium, du sulfate de potassium, de l'hydrogénocarbonate de sodium, de l'hydrogénocarbonate de potassium, du carbonate de sodium, du carbonate de potassium, du sulfate d'aluminium, du sulfate d'aluminium et de potassium (alun de potassium), du sulfate d'aluminium et de sodium (alun de sodium), de l'acétate de sodium, de l'acétate de calcium ou du formiate de calcium est utilisé pour la coagulation du latex.
  13. Procédé selon une ou plusieurs des revendications 9 à 12, dans lequel la quantité du ou des sels utilisée au total pour la coagulation du latex est de 0,5 à 200 parties en poids, de préférence de 0,8 à 80 parties en poids et de manière particulièrement préférée de 1 à 50 parties en poids, par rapport à 100 parties en poids de caoutchouc nitrile.
  14. Procédé selon une ou plusieurs des revendications 9 à 13, dans lequel le latex utilisé pour la coagulation présente une concentration en solides dans la plage allant de 1 % à 40 %, de préférence dans la plage allant de 5 % à 35 % et de manière particulièrement préférée dans la plage allant de 15 à 30 % en poids.
  15. Procédé selon une ou plusieurs des revendications 9 à 14, dans lequel la coagulation du latex est réalisée à une température dans la plage allant de 10 à 100 °C, de manière particulièrement préférée dans la plage allant de 20 à 90 °C.
  16. Procédé selon une ou plusieurs des revendications 9 à 15, dans lequel le lavage du caoutchouc nitrile coagulé est réalisé à une température dans la plage allant de 15 à 90 °C et de préférence à une température dans la plage allant de 20 à 80 °C.
  17. Procédé selon une ou plusieurs des revendications 9 à 16, dans lequel le caoutchouc nitrile obtenu est ensuite soumis à (i) uniquement une réaction de métathèse ou (ii) une réaction de métathèse et une hydrogénation ultérieure ou (iii) uniquement une hydrogénation.
  18. Caoutchoucs nitriles éventuellement hydrogénés pouvant être obtenus par le procédé selon la revendication 17.
  19. Utilisation des caoutchoucs nitriles selon une ou plusieurs des revendications 1 à 8 ou selon la revendication 18 pour la fabrication de mélanges vulcanisables.
  20. Mélange vulcanisable contenant au moins un caoutchouc nitrile selon une ou plusieurs des revendications 1 à 8 ou selon la revendication 18, au moins un agent de réticulation et éventuellement des additifs supplémentaires.
  21. Procédé de fabrication d'un mélange vulcanisable selon la revendication 20, dans lequel au moins un caoutchouc nitrile selon une ou plusieurs des revendications 1 à 8 ou selon la revendication 18, au moins un agent de réticulation et éventuellement des additifs supplémentaires sont mélangés.
  22. Procédé de fabrication de pièces moulées à base d'un caoutchouc nitrile selon une ou plusieurs des revendications 1 à 8 ou selon la revendication 18, dans lequel un mélange vulcanisable selon la revendication 20 est vulcanisé dans le cadre d'un procédé de façonnage, de préférence en utilisant un procédé de moulage par injection.
  23. Pièce moulée pouvant être obtenue par le procédé selon la revendication 22.
  24. Pièce moulée selon la revendication 23, caractérisée en ce qu'il s'agit d'un joint, d'un capuchon, d'un tuyau ou d'une membrane, notamment d'un joint torique, d'un joint plat, d'un joint d'étanchéité tournant, d'une manchette d'étanchéité, d'un capuchon d'étanchéité, d'un capuchon de protection contre la poussière, d'un joint de connecteur, d'un tuyau à isolation thermique (avec et sans ajout de PVC), d'un tuyau refroidisseur d'huile, d'un tuyau d'aspiration d'air, d'un tuyau de servo-direction ou d'une membrane de pompe.
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CN100475870C (zh) * 2005-05-20 2009-04-08 中国石油天然气集团公司 一种低腈含量交联型粉末丁腈橡胶的生产方法
DE102007024009A1 (de) * 2007-05-22 2008-11-27 Lanxess Deutschland Gmbh Mercaptangemisch
DE102007024010A1 (de) * 2007-05-22 2008-11-27 Lanxess Deutschland Gmbh Nitrilkautschuke
DE102007024011A1 (de) * 2007-05-22 2008-11-27 Lanxess Deutschland Gmbh Nitrilkautschuke

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JP5366099B2 (ja) 2013-12-11
DE102007024008A1 (de) 2008-11-27
US20080293889A1 (en) 2008-11-27
HRP20110577T1 (hr) 2011-09-30
PL2152760T3 (pl) 2011-10-31
BRPI0812147B1 (pt) 2018-11-06
MX2009012500A (es) 2009-12-09
ES2364381T3 (es) 2011-09-01
CN101679535B (zh) 2012-08-08
CN101679535A (zh) 2010-03-24
KR101180203B1 (ko) 2012-09-07
JP2010528139A (ja) 2010-08-19
RU2470950C2 (ru) 2012-12-27
WO2008142035A1 (fr) 2008-11-27
CA2685279C (fr) 2016-02-16
BRPI0812147A2 (pt) 2014-11-18
CA2685279A1 (fr) 2008-11-22
DK2152760T3 (da) 2011-08-29
KR20100022076A (ko) 2010-02-26
DE502008003433D1 (de) 2011-06-16
EP2152760A1 (fr) 2010-02-17
RU2009147302A (ru) 2011-06-27
US7923518B2 (en) 2011-04-12
PT2152760E (pt) 2011-07-08
ATE508149T1 (de) 2011-05-15

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